CN101050317A - Composite material of ultra-branched organic montmorillonite / heat vulcanization type silicon rubber, and preparation method - Google Patents
Composite material of ultra-branched organic montmorillonite / heat vulcanization type silicon rubber, and preparation method Download PDFInfo
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- CN101050317A CN101050317A CN 200710040790 CN200710040790A CN101050317A CN 101050317 A CN101050317 A CN 101050317A CN 200710040790 CN200710040790 CN 200710040790 CN 200710040790 A CN200710040790 A CN 200710040790A CN 101050317 A CN101050317 A CN 101050317A
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Abstract
This invention discloses a method for preparing hyperbranched organic montmorillonite/heat-curing silicone rubber composite. The composite is composed of: methylvinylsilicone raw rubber 80-90 parts, 2, 4-di-tert-butyl peroxy hexane 0.5-0.8 part, and hyperbranched organic montmorillonite 10-20 parts. The hyperbranched organic montmorillonite is dispersed in the polymer matrix in nanoscale lamellar state, which can exhibit good small size effect, interfacial effect and quantum tunneling effect, thus the chemical reaction contact surface area and activity of the hyperbranched organic montmorillonite are significantly increased. The composite has obviously improved tensile strength and elongation at break than silicone rubber added with organic montmorillonite. The tensile strength is near that of silicone rubber added with gaseous white carbon black.
Description
Technical field
The present invention relates to a kind of heat vulcanized silicone rubber matrix material that contains ultra-branched organic montmorillonite and preparation method thereof.
Background technology
Polynite claims montmorillenite again, is bentonitic major ingredient.Observe under electron microscope, crystal belongs to oblique system, generally is irregular sheet.Color is a white band light gray, is with light blue or light red sometimes, the gloss dimness; Have very strong adsorptive power and ion-exchange capacity, also have colloidality, plasticity-and the cohesive force of height simultaneously.Mohs' hardness 2～2.5, proportion 2～2.7g/cm
3, tap density is 1～1.1g/mL.Chemical constitution is Na
0.7(Al
3.3Mg
0.7) Si
8O
20(OH)
4NH
2O belongs to 2: 1 type layered silicates, and promptly each unit cell constitutes the sandwich-like structure by carrying an alumina octahedral wafer secretly in the middle of two silicon-oxy tetrahedron wafers, connects by shared Sauerstoffatom between the two.This tetrahedron and octahedral close-packed structure make its lattice arrangement with high-sequential, and every layer thickness is 1nm, have very high rigidity, and interlayer is easy glide not.Natural montmorillonite is laminar structured, and the about 1nm of interlamellar spacing, interlayer are the Na of hydration
+, Ca
2+Etc. commutative inorganic cation, need carry out ion-exchange, go to change the polarity of montmorillonite layer with organic cation (being intercalator), reduce the surface energy of silicate lamella, to increase by two alternate affinities.
Suitable loading capacity, excellent mechanical property and cheap price make polynite become the first-selected mineral of preparation nano composite material.
Nano composite polymer-montmorillonoid material is better than the general polymerization material in preparation method, structure, performance and application facet, has become the focus of current polymer materials fundamental research and Application and Development.Nano composite polymer-montmorillonoid material has the characteristics of following several respects: (1) preparation technology is economical and practical.The general intercalation compounding technology that adopts evenly spreads in the polymeric matrix structure lamella in the polynite, and this technology does not need to invest new high equipment, and technology is simple; (2) physical and mechanical property excellence.The intercalation compounding technology can be realized compound on nanoscale of organism matrix and inorganics disperse phase, and the nano composite polymer-montmorillonoid material of gained can ideally combine rigidity, dimensional stability and the thermostability of inorganics in toughness, workability and the dielectricity of polymkeric substance: (3) processing characteristics is good.Polymer nanocomposites melt strength height, crystallization velocity is fast, and melt viscosity is low, so injection moulding, extrudes with processing characteristicies such as blowings goodly, and the improvement of processing characteristics is significant to the practicability of nano composite polymer-montmorillonoid material.
In a word, compare with general microcosmic matrix material, the nano composite polymer-montmorillonoid material that contains a small amount of polynite shows the excellent comprehensive performance.Good performance, simple machining process and cheap price make it be with a wide range of applications in fields such as insulation material industry at various high-performance industry, agricultural and civilian tubing, automobile and component of machine, electronics and electrical equipment.
Chinese scholars has been carried out research to a certain degree to polymkeric substance (rubber)/Nano composite material of montmorillonite, and the result shows that polynite must make its intercalation or peel off in application process, could show the reinforcing property that it is unique as lamellated silicate.For example: polynite is necessary high-speed stirring in liquid polymer (rubber), necessary high-temperature fusion in solid polymer (rubber), could show the reinforcing property that it is unique, proposed special requirement in this course of processing to polymkeric substance (rubber) material, this has limited the widespread use of polynite largely.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material and preparation method, to overcome the defective of current material.
The component of ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material of the present invention and weight part are:
80～90 parts of methyl vinyl silicon kautschuks
2,0.5～0.8 part of 4-di-tert-butyl peroxide hexane
10～20 parts of ultra-branched organic montmorillonites
Methyl vinyl silicon kautschuk can adopt business-like product, as the high temperature vulcanizable silicone series product of Huitian New Material in Chemcal Engineering Co., Ltd., Shanghai's production.
2,4-di-tert-butyl peroxide hexane can adopt business-like product, as the high temperature vulcanizable silicone series product of Huitian New Material in Chemcal Engineering Co., Ltd., Shanghai's production.
Said ultra-branched organic montmorillonite is preparation like this:
1. building-up reactions monomer:
With the mixture of methyl acrylate, diethanolamine and solvent, at N
2Under the gas atmosphere, 20～40 ℃ of reaction 3～5h vacuumize then to remove and desolvate, and obtain a kind of water white transparency oily thing, i.e. N, N-dihydroxyl-3 amido methyl propionate;
Said solvent is selected from methyl alcohol, ethanol, toluene or dimethylbenzene;
The mol ratio of methyl acrylate and diethanolamine is:
Methyl acrylate: diethanolamine=1: 0.9～1.1, preferred 1: 1;
2. prepare ultra-branched organic montmorillonite:
With organo montmorillonite, step N 1., N-dihydroxyl-3 amido methyl propionate and tosic acid are under nitrogen protection, and 100～120 ℃ were reacted 8～10 hours, and collected ultra-branched organic montmorillonite then from reaction product;
The weight part of organo montmorillonite is 5～15 parts, N, and N-dihydroxyl-3 amido methyl propionate weight part is 30～50 parts, the weight part of tosic acid is 0.2～0.5 part;
Said organo montmorillonite is C for adopting intercalator
12～C
18The terminal hydroxy group quaternary ammonium salt, for example: dihydroxyl trimethyldodecane base brometo de amonio, montmorillonite modified can adopt business-like product, and the trade mark of producing as Zhejiang Feng Hong clay company limited is the product of DK2;
The preparation method of ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material of the present invention comprises the steps:
1. proportionally, that methyl vinyl silicon kautschuk and said ultra-branched organic montmorillonite is mixing in mill; Melting temperature is 20～30 ℃, and the time is 0.5～1 hour;
2. proportionally, add 2,4-di-tert-butyl peroxide hexane, 30～50 ℃ mixing 20～30 minutes, obtain film;
3. film was vulcanized 5～8 minutes at 175～185 ℃, preferably adopt vulcanizing press, can make said ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material.
Because the polynite in the ultra-branched organic montmorillonite is dispersed in the polymeric matrix with the nanometer lamella, the nanometer lamella can show excellent properties such as small-size effect, interfacial effect and quantum tunneling effect, increases the contact surface and the activity of its chemical reaction greatly.Therefore in the present invention, the tensile strength of ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material is compared with the silicon rubber of direct adding organo montmorillonite with elongation at break, has had largely to improve; And its tensile strength approaches to add the reinforcing effect of the silicon rubber of gas-phase silica, and elongation at break has also had largely and improves.
The present invention uses hyperbranched technology: (1) can solve the peel off problem of stratiform polynite in solid polymer (rubber) material; (2) can solve the dispersion problem of nano silicate lamella in material after peeling off; (3) make the surface-functionalized of nano imvite.This technology and combining nano technology are applied in the conventional industries-rubber industry of T﹠B, help the lifting of conventional industries, also help having opened the application market of nano material, so this achievement in research has far-reaching social influence and favorable economic benefit.
Embodiment
Embodiment 1
In 250mL four-necked bottle reactor, add the 0.10mol methyl acrylate, 0.10mol diethanolamine and 10mL methyl alcohol, mixture is at 15 ℃ and logical N
2Stir under the situation and be warming up to 40 ℃ behind the 30min and keep 3h, vacuumize then, obtain a kind of water white transparency oily thing, be i.e. N, N-dihydroxyl-3 amido methyl propionate to remove methyl alcohol.Take by weighing the N of 5g organo montmorillonite, 30g; N-dihydroxyl-3 amido methyl propionate monomer and 0.2g tosic acid are in four neck flasks; under nitrogen protection under 100 ℃; stirred 8 hours; vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again behind the solvent wash in washings.Throw out in 30 ℃ of following vacuum-dryings 6 hours, is obtained ultra-branched organic montmorillonite.
90 gram methyl vinyl silicon kautschuks and 10 gram ultra-branched organic montmorillonites are mixing in mill, and melting temperature is 20 ℃, and the time is 1 hour;
Add 0.5 gram 2 then, 4-di-tert-butyl peroxide hexane, 50 ℃ of slices after mixing 20 minutes are vulcanized above-mentioned film again on vulcanizing press, cure conditions is 175 ℃ * 8 minutes, promptly obtains 10% ultra-branched organic montmorillonite/heat vulcanization type silicon rubber nano composite material of the present invention.This nano composite material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 2
In 250mL four-necked bottle reactor, add the 0.20mol methyl acrylate, 0.20mol diethanolamine and 15mL methyl alcohol, mixture is at room temperature and logical N
2Stir under the situation and be warming up to 30 ℃ behind the 40min and keep 4h, vacuumize then, obtain a kind of water white transparency oily thing, be i.e. N, N-dihydroxyl-3 amido methyl propionate to remove methyl alcohol.Take by weighing the N of 10g organo montmorillonite, 40g; N-dihydroxyl-3 amido methyl propionate monomer and 0.4g tosic acid are in four neck flasks; under nitrogen protection under 110 ℃; violent stirring 9 hours; vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again behind the solvent wash in washings.Throw out in 40 ℃ of following vacuum-dryings 7 hours, is obtained ultra-branched organic montmorillonite.
85 gram methyl vinyl silicone rubbers (rubber) and 15 gram ultra-branched organic montmorillonites are mixing in mill, and melting temperature is 25 ℃, and the time is 0.8 hour;
Add 0.6 gram 2 then, 4-di-tert-butyl peroxide hexane, 40 ℃ of slices after mixing 25 minutes are vulcanized above-mentioned film again on vulcanizing press, cure conditions is 180 ℃ * 7 minutes, promptly obtains 15% ultra-branched organic montmorillonite/heat vulcanization type silicon rubber nano composite material of the present invention.This nano composite material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 3
In 250mL four-necked bottle reactor, add the 0.30mol methyl acrylate, 0.30mol diethanolamine and 20mL methyl alcohol, mixture is at room temperature and logical N
2Stir under the situation and be warming up to 20 ℃ behind the 50min and keep 5h, vacuumize then, obtain a kind of water white transparency oily thing, be i.e. N, N-dihydroxyl-3 amido methyl propionate to remove methyl alcohol.Take by weighing the N of 15g organo montmorillonite, 50g; N-dihydroxyl-3 amido methyl propionate monomer and 0.5g tosic acid are in four neck flasks; under nitrogen protection under 120 ℃; violent stirring 10 hours; vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again behind the solvent wash in washings.Throw out in 50 ℃ of following vacuum-dryings 8 hours, is obtained ultra-branched organic montmorillonite.
80 gram methyl vinyl silicone rubbers (rubber) and 20 gram ultra-branched organic montmorillonites are mixing in mill, and melting temperature is 30 ℃, and the time is 0.5 hour;
Add 0.8 gram 2 then, 4-di-tert-butyl peroxide hexane, 30 ℃ of slices after mixing 30 minutes are vulcanized above-mentioned film again on vulcanizing press, cure conditions is 185 ℃ * 5 minutes, promptly obtains 20% ultra-branched organic montmorillonite/heat vulcanization type silicon rubber nano composite material of the present invention.This nano composite material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 1
90 gram methyl vinyl silicone rubbers (rubber) and 10 gram organo montmorillonites are mixing in mill, and melting temperature is 20 ℃, and the time is 1 hour;
Add 0.5 gram 2 then, 4-di-tert-butyl peroxide hexane, 50 ℃ of slices after mixing 20 minutes are vulcanized above-mentioned film again on vulcanizing press, and cure conditions is 175 ℃ * 8 minutes, can obtain 10% organic montmorillonite/heat vulcanization type silicon rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 2
85 gram methyl vinyl silicone rubbers (rubber) and 15 gram organo montmorillonites are mixing in mill, and melting temperature is 25 ℃, and the time is 0.8 hour;
Add 0.6 gram 2 then, 4-di-tert-butyl peroxide hexane, 40 ℃ of slices after mixing 25 minutes are vulcanized above-mentioned film again on vulcanizing press, and cure conditions is 180 ℃ * 7 minutes, promptly obtains 15% organic montmorillonite/heat vulcanization type silicon rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 3
80 gram methyl vinyl silicone rubbers (rubber) and 20 gram organo montmorillonites are mixing in mill, and melting temperature is 30 ℃, and the time is 0.5 hour;
Add 0.8 gram 2 then, 4-di-tert-butyl peroxide hexane, 30 ℃ of slices after mixing 30 minutes are vulcanized above-mentioned film again on vulcanizing press, and cure conditions is 175 ℃ * 8 minutes, promptly obtains 20% organic montmorillonite/heat vulcanization type silicon rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 4
80 gram methyl vinyl silicone rubbers (rubber) and 20 gram gas-phase silicas are mixing in mill,, melting temperature is 30 ℃, the time is 0.5 hour; Add then 0.8 the gram 2,4-di-tert-butyl peroxide hexane, 30 ℃ mixing 30 minutes, slice is vulcanized above-mentioned film on vulcanizing press, cure conditions is 175 ℃ * 8 minutes, promptly obtains 20% gas-phase silica/heat vulcanized silicone rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Table 1
| Embodiment | Tensile strength (MPa) | Elongation at break (%) |
| Comparative Examples 1 | 1.10 | 260 |
| Comparative Examples 2 | 1.95 | 280 |
| Comparative Examples 3 | 2.65 | 320 |
| Comparative Examples 4 | 3.95 | 380 |
| Embodiment 1 | 2.05 | 390 |
| Embodiment 2 | 2.95 | 410 |
| Embodiment 3 | 3.90 | 420 |
Claims (8)
1. a ultra-branched organic montmorillonite is preparation like this, it is characterized in that:
1. building-up reactions monomer:
With the mixture of methyl acrylate, diethanolamine and solvent, at N
2Under the gas atmosphere, 20～40 ℃ of reaction 3～5h vacuumize then to remove and desolvate, and obtain N, N-dihydroxyl-3 amido methyl propionate;
2. prepare ultra-branched organic montmorillonite:
With organo montmorillonite, step N 1., N-dihydroxyl-3 amido methyl propionate and tosic acid are under nitrogen protection, and 100～120 ℃ were reacted 8～10 hours, and collected ultra-branched organic montmorillonite then from reaction product.
2. ultra-branched organic montmorillonite according to claim 1 is characterized in that said solvent is selected from methyl alcohol, ethanol, toluene or dimethylbenzene.
3. ultra-branched organic montmorillonite according to claim 1 is characterized in that, the mol ratio of methyl acrylate and diethanolamine is: methyl acrylate: diethanolamine=1: 0.9～1.1.
4. ultra-branched organic montmorillonite according to claim 3 is characterized in that, the mol ratio of methyl acrylate and diethanolamine is: methyl acrylate: diethanolamine=1: 1.
5. ultra-branched organic montmorillonite according to claim 1 is characterized in that, the weight part of organo montmorillonite is 5～15 parts, N, and N-dihydroxyl-3 amido methyl propionate weight part is 30～50 parts, the weight part of tosic acid is 0.2～0.5 part.
6. ultra-branched organic montmorillonite according to claim 1 is characterized in that, said organo montmorillonite is C for adopting intercalator
12～C
18The organo montmorillonite that terminal hydroxy group is quaternary ammonium salt-modified.
7. ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material, component and weight part are:
80～90 parts of methyl vinyl silicon kautschuks
2,0.5～0.8 part of 4-di-tert-butyl peroxide hexane
10～20 parts of ultra-branched organic montmorillonites
Wherein: ultra-branched organic montmorillonite is each described ultra-branched organic montmorillonite of claim 1～6.
8. prepare the method for the described ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material of claim 7, comprise the steps:
1. proportionally, methyl vinyl silicon kautschuk and said ultra-branched organic montmorillonite is mixing in mill; Melting temperature is 20～30 ℃, and the time is 0.5～1 hour;
2. proportionally, add 2,4-di-tert-butyl peroxide hexane, 30～50 ℃ mixing 20～30 minutes, obtain film;
3. film was vulcanized 5～8 minutes at 175～185 ℃, make said ultra-branched organic montmorillonite/heat vulcanization type silicon rubber matrix material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504539A (en) * | 2011-10-24 | 2012-06-20 | 中特华星电缆股份有限公司 | Nanometer montmorillonoid modified silicon rubber and preparation method thereof |
| CN103834197A (en) * | 2014-03-18 | 2014-06-04 | 上海工程技术大学 | Preparation method of organic montmorillonite modified by supermolecular liquid crystal polymer |
| CN112592619A (en) * | 2020-12-22 | 2021-04-02 | 闫明亮 | Antibacterial and mildew-proof putty powder and preparation method thereof |
| CN114591556A (en) * | 2022-03-25 | 2022-06-07 | 安庆市悦发管业有限公司 | Corrosion-resistant directional polyethylene composite pipe |
-
2007
- 2007-05-17 CN CN 200710040790 patent/CN101050317A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504539A (en) * | 2011-10-24 | 2012-06-20 | 中特华星电缆股份有限公司 | Nanometer montmorillonoid modified silicon rubber and preparation method thereof |
| CN103834197A (en) * | 2014-03-18 | 2014-06-04 | 上海工程技术大学 | Preparation method of organic montmorillonite modified by supermolecular liquid crystal polymer |
| CN112592619A (en) * | 2020-12-22 | 2021-04-02 | 闫明亮 | Antibacterial and mildew-proof putty powder and preparation method thereof |
| CN114591556A (en) * | 2022-03-25 | 2022-06-07 | 安庆市悦发管业有限公司 | Corrosion-resistant directional polyethylene composite pipe |
| CN114591556B (en) * | 2022-03-25 | 2023-05-09 | 安庆市悦发管业有限公司 | Corrosion-resistant oriented polyethylene composite pipe |
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